Preparation and Characterization of Luminescent SCS and NCN

Jun 29, 2006 - Preparation and Characterization of Luminescent SCS and NCN Pincer Platinum Complexes Derived from 3,5-Bis(anilinothiocarbonyl)toluene...
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Notes Preparation and Characterization of Luminescent SCS and NCN Pincer Platinum Complexes Derived from 3,5-Bis(anilinothiocarbonyl)toluene Ken Okamoto, Takaki Kanbara,* Takakazu Yamamoto,* and Akihide Wada Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama, 226-8503 Japan ReceiVed January 6, 2006 Summary: Starting from 5-methyl-1,3-bis(anilinothiocarbonyl)benzene (1), two types of luminescent pincer platinum complexes with κ3S,C,S and κ3N,C,N coordination modes were obtained. Reaction of 1 with K2PtCl4 afforded a pincer Pt(II) complex (3) with the κ3S,C,S coordination mode, whereas oxidatiVe cyclization of 1 yielded 5-methyl-1,3-bis(benzothiazol-2-yl)benzene (2), which proVided a pincer Pt(II) complex (4) with the κ3N,C,N coordination mode. Molecular structures and photochemical properties of the complexes haVe been examined. The decay lifetimes of the emission from the complexes were in the range 10-5-10-6 s, which were indicatiVe of phosphorescent emission.

Scheme 1. New Pincer Pt(II) Complexes 3 and 4 Derived from 1

Introduction Square-planar cycloplatinated complexes are often light emissive,1 and use of such light emissive metal complexes, especially phosphorescent metal complexes, as emitters in lightemitting diodes (LEDs) has attracted much attention.2 * Corresponding authors. E-mail: [email protected]. Fax: +8145-924-5976. (1) (a) Brooks, J.; Babayan, Y.; Lamansky, S.; Djurovich, P. I.; Tsyba, I.; Bau, R.; Thompson, M. E. Inorg. Chem. 2002, 41, 3055. (b) Balashev, K. P.; Puzyk, M. V.; Kotlyar, V. S.; Kulikova, M. V. Coord. Chem. ReV. 1997, 109, 159. (c) Maestri, M.; Deuschel-Cornioley, C.; von Zelewsky, A. Coord. Chem. ReV. 1991, 111, 117. (d) Liu, Q.; Thorne, L.; Kozin, I.; Song, D.; Seward, C.; D’Iorio, M.; Tao, Y.; Wang, S. J. Chem. Soc., Dalton Trans. 2002, 3234. (e) Cheung, T.-C.; Cheung, K.-K.; Peng, S.-M.; Che, C.-M. J. Chem. Soc., Dalton Trans. 1996 1645. (f) Lu, W.; Mi, B.-X.; Chan, M. C.-W.; Hui, Z.; Zhu, N.; Lee, S.-T.; Che, C.-M. Chem. Commun. 2002, 206. (g) Lai, S.-W.; Chan, M. C.-W.; Cheung, T.-C.; Peng, S.-M.; Che, C.-M. Inorg. Chem. 1999, 38, 4046. (h) Lai, S.-W.; Chan, M. C.-W.; Cheung, K.-K.; Che, C.-M. Organometallics 1999, 18, 3327. (i) Yam, V. W.-W.; Tang, R. P.-L.; Wong, K. M.-C.; Lu, W. X.-X.; Cheung, K.-K.; Zhu, N. Chem. Eur. J. 2002, 8, 4066. (j) Williams, J. A. G.; Beeby, A.; Davies, E. S.; Weinstein, J. A.; Wilson, C. Inorg. Chem. 2003, 42, 8609. (k) Lu, W.; Mi, B.-X.; Chan, M. C. W.; Hui, Z.; Che, C.-M.; Zhu, N.; Lee, S.-T. J. Am. Chem. Soc. 2004, 126, 4958. (l) Lu, W.; Chan, M. C. W.; Zhu, N.; Che, C.-M.; Li, C.; Hui, Z. J. Am. Chem. Soc. 2004, 126, 7639. (m) Chiu, B. K.-W.; Lam, M. H.-W.; Lee, D. Y.-K.; Wong, W.-Y. J. Organomet. Chem. 2004, 689, 2888. (n) Jude, H.; Bauer, J. A. K.; Connick, W. B. Inorg. Chem. 2004, 43, 725. (o) Jude, H.; Bauer, J. A. K.; Connick, W. B. Inorg. Chem. 2002, 41, 2275. (p) Kanbara, T.; Yamamoto, T. J. Organomet. Chem. 2003, 688, 15. (q) Kanbara, T.; Okada, K.; Yamamoto, T.; Ogawa, H.; Inoue, T. J. Organomet. Chem. 2004, 689, 1860. (r) Jude, H.; Bauer, J. A. K.; Connick, W. B. Inorg. Chem. 2005, 44, 1211. (s) Farley, S. J.; Rochester, D. L.; Thompson, A. L.; Howard, J. A. K.; Williams, J. A. G. Inorg. Chem. 2005, 44, 9690. (t) Sotoyama, W.; Satoh, T.; Sato, H.; Matsuura, A.; Sawatari, N. J. Phys. Chem. A 2005, 109, 9760. (2) (a) Baldo, M. A.; Thompson, M. E.; Forrest, S. R. Pure Appl. Chem. 1999, 71, 2095. (b) Richter, M. M. Chem. ReV. 2004, 104, 3003. (c) Holder, E.; Langeveld, B. M. W.; Schubert, U. S. AdV. Mater. 2005, 17, 1109, and references therein.

We previously reported that κ3S,C,S pincer Pt(II) complexes containing tertiary thioamide-based pincer ligands exhibited strong phosphorescent emission in the glassy frozen state and in the solid state.1q We have extended the research and now report that the secondary thioamide compound 1 is a good starting material to afford the two new pincer Pt(II) complexes 3 and 4. Secondary thioamides have been used in the field of medical and organic chemistry,3,4 and it is known that oxidative cyclization of secondary N-arylthioamides with K3[Fe(CN)6] gives benzothiazole derivatives.4 Such a cyclization reaction can proceed with bis(secondary thioamide)s, and 1 can be transformed into 2; thus, from the ligands 1 and 2, the new complexes 3 and 4 are obtained. Consequently, expansion of the complex synthesis exhibited in Scheme 1 by modifying the aromatic groups in 1 is expected to give various Pt complexes of the types 3 and 4. Cyclometalated κ2C,N Ir(III) and Pt(II) complexes of 2-arylbenzothiazoles1a,2c and related κ3N,N,N type metal complexes of neutral tridentate ligands such as 2,6-bis(benzothiazol(3) (a) Jagodzin˜ski, T. S. Chem. ReV. 2003, 103, 197. (b) Klingele, M. H.; Brooker, S. Eur. J. Org. Chem. 2004, 3422. (c) Murai, T.; Aso, H.; Tatematsu, Y.; Itoh, Y.; Niwa, H.; Kato, S. J. Org. Chem. 2003, 68, 8514. (d) Ach, D.; Reboul, V.; Metzner, P. Eur. J. Org. Chem. 2002, 2573. (e) Ares, J. J. Synth. Commun. 1991, 21, 625. (f) Tamaru, Y.; Kagotani, M.; Yoshida, Z. Tetrahedron Lett. 1981, 35, 3409. (4) (a) Petrova, D.; Jakopc´ic´, K. Croatica Chem. Acta 1976, 48, 319 (b) Downer, N. K.; Jackson, Y. A. Org. Biomol. Chem. 2004, 2, 3039. (c) Mathis, C. A.; Wang, Y.; Holt, D. P.; Huang, G.-F.; Debnath, M. L.; Klunk, W. E. J. Med. Chem. 2003, 46, 2740.

10.1021/om060016j CCC: $33.50 © 2006 American Chemical Society Publication on Web 06/29/2006

Notes

Organometallics, Vol. 25, No. 16, 2006 4027 Table 1. Selected Bond Lengths and Bond Angles for 1-4 Bond Lengths (Å) 1 Pt-C Pt-Cl C-S C-S C(S)-N C(S)-N

1.671(2) 1.331(2)

3 1.957(7) 2.389(2) 1.700(7) 1.714(7) 1.31(1) 1.32(1)

2

4

1.728(8) 1.768(6) 1.311(9) 1.190(9)

1.924(5) 2.4254(14) 1.712(5) 1.724(5) 1.349(7) 1.327(7)

Bond Angles (deg) Cl-Pt-C S-Pt-S N-Pt-N

Figure 1. X-ray crystal structures of (a) 3 and (b) 4 with thermal ellipsoids drawn at the 50% probability level. Hydrogen atoms and solvated molecules are omitted for simplicity.

2-yl)pyridine have been reported.5 However, a κ3N,C,N pincer complex such as 4 constituted of the benzothiazole unit has not yet been reported to our knowledge. On this basis, we here report that 1 can give two luminescent pincer Pt(II) complexes, 3 and 4, which are composed of different donor sets with κ3S,C,S and κ3N,C,N pincer coordination modes, respectively. Molecular structures and photochemical properties of the complexes are also described.

Results and Discussion Preparation of 1 is described in the Experimental Section. The oxidative cyclization of 1 using K3[Fe(CN)6] afforded 2. Reactions of 1 and 2 with K2PtCl4 in acetic acid led to regioselective ortho,ortho-cycloplatination at the C-2 position of the centered benzene ring with Pt(II) and afforded the corresponding pincer complexes 3 and 4 in 63 and 51% yields, respectively. 3 and 4 were fairly stable to air and water and were thermally stable up to 300 °C. 3 showed good solubility in polar organic solvents such as MeOH, EtOH, DMF, and DMSO. 4 was less soluble and showed only low solubility in CH2Cl2 and CHCl3. The 1H NMR spectra of 3 and 4 shown in Figure S1 agree with their structures. In the 13C NMR spectrum of 3, the ortho,orthocycloplatinated carbon (Cipso) was shifted to a higher magnetic field by 24 ppm according to the σ-bonding to Pt. The ORTEP drawings of 3 and 4 are presented in Figure 1, and selected bond lengths and bond angles of 1-4 are summarized in Table 1. 3 and 4 have a distorted square-planar geometry similar to each other. As shown in Figure 1a, 3 has a κ3S,C,S pincer complex strucrture, similar to previously reported thioamide-based pincer complexes.1q,6 The Pt-C and Pt-Cl bond lengths are consistent with those of the reported thioamide-based pincer Pt(II) complexes. The CdS bond lengths are longer than those observed with 1, and the C(S)-N bond (5) (a) Boc´a, M.; Boc´a, R.; Kickelbick, G.; Linert, W.; Svoboda, I.; Fuess, H. Inorg. Chem. Acta 2002, 338, 36. (b) Ru¨ttimann, S.; Moreau, C. M.; Williams, A. F. Polyhedron 1992, 11, 635. (c) Addison, A. W.; Burman, S.; Wahlgren, C. G. J. Chem. Soc., Dalton Trans. 1987, 2621. (d) Livingstone, S. E.; Nolan, J. D. J. Chem. Soc., Dalton Trans. 1972, 218.

3

4

178.76(17) 170.77(6)

177.72(16) 158.57(18)

lengths are somewhat shorter than those observed with 1, indicating that the S-coordination to Pt decreases the doublebond character of the CdS bond. Two DMSO molecules in the crystal are hydrogen bonded to the N-H protons of 3 through the O of DMSO (N‚‚‚O ) 2.809 and 2.852 Å), in agreement with known hydrogen-bonding donor ability of the N-H hydrogen of the secondary thioamide.7 As depicted in Figure 1b, 4 has a κ3N,C,N coordination mode. The Pt-C bond length is shorter than those in 3 and related pincer Pt(II) complexes.1e,8 The cycloplatination brings about a close contact between the H(4′) hydrogen of the benzothiazole ring and the Cl ligand in 4, as depicted in Scheme 1, and distances of 2.66 and 2.70 Å are obtained for the distance between H(4′) and Cl by X-ray crystallography. The distance is smaller than the sum (2.95 Å) of the van der Waals radii of H and Cl, indicating the presence of an intramolecular hydrogen bonding interaction between H(4′) and Cl.9 The two benzothiazole rings are nearly parallel to the center benzene ring. The intramolecular hydrogen-bonding interaction agrees with a 1H NMR shift of the H(4′) hydrogen peak of 2 to a lower magnetic field by 1.77 ppm by the complexation with Pt, as shown in Figure S1. The crystal-packing diagrams of 3 and 4 exhibit that the complexes are stacked in a head-to-tail fashion with interplanar distances of 3.56 and 3.40 Å for 3 and 4, respectively, as depicted in Figure S4. The molecular planes are slipped and the Pt‚‚‚Pt distances between Pt in the upper complex and Pt in the lower complex are 6.00 and 5.51 Å for 3 and 4, respectively. These data indicate that there is no significant d8-d8 interaction. Electrochemical Response. Redox behavior of 3 and 4 has been investigated by cyclic voltammetry, and the data are given in Table 2. Electrochemical reduction of 3 occurs at -1.78 V vs Cp2Fe+/Cp2Fe, which is considered to occur mainly at the ligand. The reduction peak is located at a higher potential than that of 1 (Epred ) -2.38 V), presumably due to bonding to (6) (a) Takahashi, S.; Nonoyama, M.; Kita, M. Transition Met. Chem. 1995, 20, 528. (b) Nojima, Y.; Nonoyama, M.; Nakajima, K. Polyhedron 1996, 15, 3795. (c) Hossain, M. A.; Lucarini, S.; Powell, D.; BowmanJames, K. Inorg. Chem. 2004, 43, 7275. (d) Akaiwa, M.; Kanbara, T.; Fukumoto, H.; Yamamoto, T. J. Organomet. Chem. 2005, 690, 4192. (e) Begum, R. A.; Powell, D.; Bowman-James, K. Inorg. Chem. 2006, 45, 964. (7) (a) Lee, H.-J.; Choi, Y.-S.; Lee, K.-B.; Park, J.; Yoon, C.-J. J. Phys. Chem. A. 2002, 106, 7010. (b) Inoue, Y.; Kanbara, T.; Yamamoto, T. Tetrahedron Lett. 2003, 44, 5167. (8) (a) Albrecht, M.; van Koten, G. Angew. Chem., Int. Ed. 2001, 40, 3750. (b) Albrecht, M.; Spek, A. L.; van Koten, G. J. Am. Chem. Soc. 2001, 123, 7233. (c) Steenwinkel, P.; Gossage, R. A.; van Koten, G. Chem. Eur. J. 1998, 4, 759, and references therein. (9) (a) Brammer, L.; Bruton, E. A.; Sherwood, P. Cryst. Growth Des. 2001, 1, 277. (b) Thallapally, P. K.; Nangia, A. CrystEngComm 2001, 27, 1.

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Notes

Table 2. Photochemical, Electrochemical, and Thermal Data of 3 and 4 3 absorptiona (UV-vis) λmax/nm (, M-1 cm-1) emission (PL) λmax/nmb λmax/nmc λmax/nmd φfe τ/µsf Epred/Vg Epox/Vg Td10/°Ch

294 (25 300) 383 (5900) 425 (6400) 478 (11 100) 544 (1300) 631 741 0.08 3.7 -1.78 0.64 331

4 321 (23 800) 388 (5900) 425(8300) 449 (12 800) 550, 597, 649, 717sh 550, 597, 649, 718sh 702 0.33 9.4 (4.1) -1.98 326

a

In THF. The values in the parentheses are molar absorption coefficients. b In a CH Cl -THF (3:2) matrix at 77 K. c In a CH Cl -THF (3:2) solution 2 2 2 2 at 298 K. d For a microcrystalline sample at 298 K. e Quantum yield in a CH2Cl2-THF (3:2) matrix at 77 K. fac-Tris(2-phenylpyridine)iridium (φf ) 0.4 ( 0.1) was used as a reference.13 f Emission decay lifetime at 77 K and that at 298 K in parentheses. g Electrochemical oxidation and reduction peak current potentials vs Cp2Fe+/Cp2Fe. Measured in a THF solution of [(n-Bu)4N][BF4] (0.10 M). h Temperature for 10% weight loss under N2.

Figure 3. Excitation and emission spectra of (a) 3 and (b) 4 in a frozen matrix of CH2Cl2-THF (3:2) at 77 K.

Figure 2. UV-vis spectra of the ligands and the complexes in THF at room temperature: (a) 1 and 3; (b) 2 and 4.

electron-donating Pt. The oxidation of 3 with Epox of 0.64 V is considered to take place mainly at Pt, because 1 is oxidized at a considerably higher positive potential (Epox ) 1.01 V). 4 exhibits a reduction peak at -1.98 V, and the reduction potential is also at a higher potential than that of 2 (Epred ) -2.49 V). However, oxidation of 2 and 4 was not observed up to 1.2 V. Optical Data. Figure 2 shows absorption spectra of 1-4. The strong absorption bands around 300 nm are attributed to a π-π* transition in the ligands. 1 exhibits a tail absorption in the range 380-500 nm, which is assigned to an n-π* transition in the thioamide group.10,11 Absorption spectra of 3 and 4 show (10) (a) Petiau, M.; Fabion, J. THEOCHEM 2001, 538, 253. (b) Olszewska, T.; Gdaniec, M.; Polon´ski, T. J. Org. Chem. 2004, 69, 1248. (11) Dimitra, K.-D.; Paras, N. Y.; Mavroudis, A. D.; Mauro, C. J. Inorg. Biochem. 2000, 78, 347.

overlapped absorption bands in the region 400-500 nm, and the shape of the spectra in the region is similar to that of reported cycloplatinated complexes.1j,s,11 Absorption bands of similar Pt complexes in this region have been assigned to metal-to-ligand charge-transfer (MLCT) transitions.1q,t The position of the UVvis peak of 3 roughly agrees with the difference between the electrochemical oxidation and reduction potentials of 3 (0.64 - (-1.98) ) 2.62 V or 21 000 cm-1) and supports the assignment of the UV-vis band to the MLCT band. The UVvis peak of 3 at about 470 nm exhibits solvatochromism, as shown in Table S1; such solvatochromism is often observed for charge-transfer bands and gives additional support for the assignment to the MLCT band.12 3 and 4 were photoluminescent in a glassy frozen state and in the solid; 4 was light emissive even in solutions at room temperature. The photoluminescence data of 3 and 4 are included in Table 2, and Figure 3 shows photoluminescence spectra of 3 and 4. As seen from Figure 3a, 3 shows a broad emission band at about 630 nm when excited with 455 nm light in the glassy frozen state at 77 K. The emission peak is located at a longer wavelength than the onset position of the UV-vis absorption band at about 580 nm, and the emission gives a decay lifetime (τ) of 3.7 µs in the glassy state. These data are indicative of phosphorescent emission. The emission spectrum and lifetime τ of 3 are similar to those of reported tertiary thioamide-based pincer Pt(II) complexes,1q and the reported emission of the Pt(II) complexes has been assigned to the emission occurring from a 3MLCT excited state. A microcrystalline sample of 3 exhibited (12) (a) Chen, P.; Meyer, T. J. Chem. ReV. 1998, 98, 1439. (b) Hissler, M.; Connick, W. B.; Geiger, D. K.; McGarrah, J. E.; Lipa, D.; Lachicotte, R. J.; Eisenberg, R. Inorg. Chem. 2000, 39, 447. (c) Pomestchenko, I. E.; Luman, C. R.; Hissler, M.; Ziessel, R.; Castellano, F. N. Inorg. Chem. 2003, 42, 1394.

Notes

Organometallics, Vol. 25, No. 16, 2006 4029

a weak emission at about 740 nm at room temperature, which was significantly red-shifted from that observed in the glassy frozen state, suggesting stabilization of the excited state by formation of excimer-like adduct(s) in the solid.14 The layerto-layer packed structure of 3 seems to be suited for the formation of such an adduct in the solid. As shown in Figure 3b, 4 in the glassy frozen state exhibits a vibronic-structured emission band in the range 530-750 nm, with a spacing of about 1400 ( 60 cm-1, which corresponds to skeletal vibrational frequencies of the benzothiazole ligand.1a,i,j Essentially the same emission spectrum was obtained at room temperature, as depicted in Figure S5. The emission peak of 4 also deviates from the onset position of the UV-vis absorption band. 4 gave long lifetimes of 9.4 and 4.1 µs in the glassy frozen state and in a 3:2 mixture of CH2Cl2 and THF at room temperature, respectively. The large Stokes shift and the relatively long lifetime suggest that the emission of 4 is also a phosphorescent emission. With reference to previous spectroscopic studies on related pincer Pt(II) complexes such as [5-methyl-1,3-di(2-pyridyl)phenyl-C2,N,N′]chloroplatinum(II) (5),1j the emission from 4 would be assigned to a ligand-centered 3(π*π) transition. The excitation and emission peaks of 4 were observed in a lower energy region by about 1620 cm-1 than those of 5, suggesting that the expansion of the aromatic system in the ligand resulted in the reduction of the band gap. In the solid state, the emission peak of 4 was red-shifted to about 700 nm, which was also related to the layer-to-layer stacking of the complex in the solid.

Conclusion and Scope S-Coordinating and oxidative cyclization ability of 1 provided two phosphorescent pincer Pt(II) complexes, 3 and 4, with different κ3S,C,S and κ3N,C,N coordination systems. The electrochemical, UV-vis, and photoluminescence data support a notion that the emission from 3 originates from the 3MLCT excited state. On the other hand, the emission from 4 is considered to originate from 3(π*π) emission. By modifying the structure of the starting material 1, various new Pt complexes of the types 3 and 4 are considered to be obtained, and the chemistry of the luminescent pincer complexes is expected to be expanded.

Experimental Section Synthesis of 5-Methyl-1,3-bis(anilinothiocarbonyl)benzene (1). To magnesium powder (255 mg, 10.5 mmol) was added dropwise a THF (5 mL) solution of 3,5-dibromotoluene (1.25 g, 5 mmol). The reaction mixture was refluxed under N2 for 12 h. The resulting mixture was allowed to cool at 0 °C, and a THF (5 mL) solution of phenylisothiocyanate (1.35 g, 10 mmol) was added. The reaction (13) King, K. A.; Spellane, P. J.; Watts, R. J. J. Am. Chem. Soc. 1985, 107, 1431. (14) Delahaye, S.; Loosli, C.; Liu, S.-X.; Decurtins, S.; Labat, G.; Neels, A.; Loosli, A.; Ward, T. R.; Hauser, A. AdV. Funct. Mater. 2006, 16, 286, and references therein.

mixture was stirred for 24 h at room temperature. After water was added, the resulting yellow precipitate was collected by filtration. The precipitate was washed with chloroform and ether (543 mg, 30% yield). FAB-mass: m/z 363 [M + H]+. 1H NMR (400 MHz in DMSOd6): δ 11.83 (s, 2H), 8.03 (s, 1H), 7.81-7.80 (m, 6H), 7.44 (t, J ) 7.2 Hz, 4H), 7.28 (t, J ) 7.2 Hz, 2H), 2.46 (s, 3H). 13C NMR (100 MHz in DMSO-d6): δ 196.7, 142.2, 140.0, 137.3, 130.3, 128.5, 126.4, 124.2, 123.5, 21.0. Anal. Calcd for C21H18N2S2: C, 69.58; H, 5.00; N, 7.73; S, 17.69. Found: C, 69.55; H, 4.85; N, 7.57; S, 17.42. Synthesis of 5-Methyl-1,3-bis(2-benzothiazolyl)benzene (2). To a suspension of 1 (181 mg, 0.5 mmol) in ethanol (1 mL) was added a 30% solution of aqueous NaOH (1 mL). The solution was added dropwise to freshly prepared aqueous potassium ferricyanide (1.317 g, 4.0 mmol) at 80 °C, and the reaction mixture was stirred at 80 °C for 30 min. After cooling to room temperature, the precipitate was washed thoroughly with water to give a pale yellow powder of 2 (116 mg, 65% yield). FAB-mass: m/z 359 [M + H]+. 1H NMR (400 MHz in CDCl3): δ 8.55 (s, 1H), 8.11 (d, J ) 7.6 Hz, 2H), 8.07 (s, 2H), 7.94 (d, J ) 7.2 Hz, 2H), 7.52 (s, 2H), 7.42 (t, J ) 7.6 Hz, 2H), 2.56 (s, 3H). 13C NMR (100 MHz in CDCl ): δ 167.1, 154.0, 139.8, 135.1, 3 134.4, 130.3, 126.4, 125.3, 123.3, 121.6, 21.6. Anal. Calcd for C21H14N2S2: C, 70.36; H, 3.98; N, 7.81; S, 17.89. Found: C, 70.49; H, 3.94; N, 7.46; S, 17.39. Synthesis of [5-Methyl-1,3-bis(anilinothiocarbonyl)phenylC2,S,S′]chloroplatinum(II) (3). A mixture of 1 (36 mg, 0.1 mmol) and K2PtCl4 (41 mg, 0.1 mmol) in acetic acid (3 mL) was refluxed for 72 h under N2. The resulting orange precipitate was filtered and washed with methanol and water to give a bright reddish powder of 3 (38 mg, 63% yield). FAB-mass: m/z 556 [M - Cl]+. 1H NMR (400 MHz in DMSOd6): δ 12.09 (s, 2H), 8.04 (s, 2H), 7.46-7.63 (m, 10H), 2.34 (s, 3H). 13C NMR (100 MHz in DMSO-d6): δ 202.2, 161.2, 153.9, 143.2, 137.4, 129.2, 129.1, 128.2, 125.6, 20.5. Anal. Calcd for C21H17ClN2PtS2: C, 42.60; H, 2.89; N, 4.73; Cl, 5.99; S, 10.83. Found: C, 42.03; H, 2.89; N, 4.40; Cl, 5.96; S, 11.17. Synthesis of [5-Methyl-1,3-bis(2-benzothiazolyl)phenyl-C2,N,N′]chloroplatinum(II) (4). Preparation of 4 was carried out in analogy with that of 3 using 2 to afford a yellow powder of 4 (51% yield). FAB-mass: m/z 587 [M + H]+, 552 [M - Cl]+. 1H NMR (400 MHz in CDCl3): δ 9.88 (d, J ) 8.8 Hz, 2H), 7.83 (d, J ) 8.0 Hz, 2H), 7.66 (t, J ) 8.0 Hz, 2H), 7.47 (t, J ) 8.8 Hz, 2H), 7.39 (s, 2H), 2.36 (s, 3H). Anal. Calcd for C21H13ClN2PtS2: C, 42.90; H, 2.23; N, 4.76; Cl, 6.03; S, 10.91. Found: C, 42.91; H, 2.51; N, 4.42; Cl, 6.23; S, 10.23.

Acknowledgment. The authors gratefully thank Dr. T. Koizumi of our laboratory for his experimental support. This work has been partly supported by a Grant-in-Aid from the Ministry of Education, Science, Sports, and Culture of Japan. Supporting Information Available: General procedures, X-ray crystallographic data, 1H NMR spectra, and UV-vis and photoluminescence data. This material is available free of charge via the Internet at http://pubs.acs.org. OM060016J